Synthesis of All-Trans High Molecular Weight Poly(N-alkylcarbazole-2,7-vinylene)s and Poly(9,9-dialkylfluorene-2,7-vinylene)s by Acyclic Diene Metathesis (ADMET) Polymerization Using Ruthenium−Carbene Complex Catalysts

Abstract

Syntheses of poly(9,9-dialkylfluorene-2,7-vinylene)s (PFVs, alkyl = n-hexyl, n-octyl, 2′-ethylhexyl) and poly(N-alkylcarbazole-2,7-vinylene)s (PCVs, alkyl = n-octyl, 9′-heptadecanyl) by acyclic diene metathesis (ADMET) polymerization using Ru−carbene complexes have been explored. The polymerizations in the presence of Ru(CHPh)(Cl)2(IMesH2)(PCy3) and Ru(CH-2-OiPr-C6H4)(Cl)2(IMesH2) [Cy = cyclohexyl, IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] afforded relatively high molecular weight PFVs, PCV (alkyl = 9′-heptadecanyl) with unimodal molecular weight distributions, and the olefinic double bonds in the resultant polymers possessed highly trans regularity in all cases. The resultant defect-free PFVs possessed higher absolute quantum yields (Φ = 92−99%) than those reported previously, whereas no significant differences in the UV−vis and the fluorescent spectra (absorption bands, peak maxima) in the resultant PFVs were observed as an effect of alkyl side chain in the 9-position. The UV−vis an...